JPH0723353B2 - 5-Substituted amino-1-hydroxy-2-naphthoic acid aryl compound - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to an aryl 2-naphthoate compound, particularly as a synthetic intermediate for a cyan dye-forming coupler in a silver halide color photographic light-sensitive material, and a red light or infrared light. The present invention relates to a polymerizable 5-substituted amino-1-hydroxy-2-naphthoic acid aryl compound as a synthetic intermediate of an indophenol dye having light absorption.

(Prior Art) After exposing a silver halide color photographic light-sensitive material to color development, an aromatic primary amine developing agent oxidized by color development reacts with a dye-forming coupler to form a color image. In this color image forming system, a color reproduction method by a subtractive color method is generally used, and in order to reproduce blue, green, and red, color images of yellow, magenta, and cyan having complementary colors are formed. . Among them, phenol derivatives and naphthol derivatives have been widely used as cyan dye-forming couplers. However, the thermal fastness of the color image by the indophenol dye obtained from these phenol derivatives and naphthol derivatives is low,
Further, there is a defect that a color image is likely to undergo reduction and fading when treated with a tired bleaching solution or a bleach-fixing solution. Therefore, in order to improve these drawbacks, a 1-naphthol type coupler having a substituted amino group at the 5-position has been proposed. For example, JP-A-60-237448, JP-A-61-153640 and JP-A-61-1455.
The coupler disclosed in No. 57. further,
The indophenol dyes obtained from these couplers are much more robust than the conventional indophenol dyes, and their absorption ranges from red light to infrared light. For example, dyes for filters and semiconductor lasers were used. It is also useful as a dye for recording materials.

JP-A-60-237448, JP-A-61-153640 and JP-A-60-14.
According to No. 5557, among various substituents at the 5-position, a 1-naphthol type coupler substituted with an oxycarbonylamino group or a sulfonamide group is particularly preferable.
However, these synthetic methods (hereinafter referred to as conventional methods) are carried out by reacting 5-amino-1-hydroxy-2-naphthoic acid with trifluoroacetic anhydride to give amino acids as 1-hydroxy-5-trifluoroacetamido-2-naphthoic acid. After protecting the group, it is converted to p-nitrophenyl ester, and then the carboxyl group at the 2-position is amidated by reaction with alkylamine. After that, the trifluoroacetamide group is hydrolyzed to give 5-amino-1-hydroxy. -2-
This is a method of obtaining a naphthoic acid amide and then reacting it with a chloroformic acid ester or a sulfonyl chloride to obtain a target coupler.

(Problems to be Solved by the Invention) However, the above-mentioned conventional method not only has many steps, but also uses trifluoroacetic anhydride, which is expensive and inferior in supplyability, merely as a protecting group, which is not always preferable (for example, Synthesis Examples of Exemplified Coupler (3) in Kai Sho 60-237448 and Exemplified Coupler (6) in JP-A 61-153640
Synthesis example). The scheme of synthesizing the coupler by this conventional method is illustrated below.

An object of the present invention is to provide a 5-substituted amino-1-naphthol type coupler, and further, a novel intermediate which enables an indophenol dye derived therefrom to be synthesized with less steps and at low cost. To do.

(Means for Solving the Problems) The object of the present invention is achieved by an aryl 2-naphthoate compound represented by the following formula.

(In the formula, R ₁ represents an oxycarbonyl group or a sulfonyl group selected from the group consisting of an alkoxycarbonyl group having 2 to 13 carbon atoms, a methanesulfonyl group and a p-toluenesulfonyl group, and Ar represents an unsubstituted phenyl group or It represents a nitrophenyl group.) By using the 2-naphthoic acid aryl compound (I) of the present invention, a 5-substituted amino-1-naphthol type coupler (II) can be synthesized at a low cost in a short process as described below. In addition, it is possible to induce an indophenol dye by a coupling reaction with an oxidation product of an aromatic primary amine (for example, a paraphenylenediamine derivative or a paraaminophenol derivative) or a condensation reaction of an aromatic nitrilo compound.

(In the formula, R ₁ and Ar have the same meanings as described above, and R represents a substituent such as an alkyl group and an aryl group.) Next, the compound of the present invention will be described in detail.

In formula (I), R ₁ is an alkoxycarbonyl group having 2 to 13 carbon atoms which may be substituted with a halogen atom, an aryl group, an alkenyl group, an alkynyl group, an alkoxy group, an alkylthio group or an aryloxy group (examples of alkyl groups As a methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, t-butyl group, n-pentyl group, n-hexyl group, cyclohexyl group, n-heptyl group, n-octyl group, 2-ethylhexyl group, n-nonyl group, n-decyl group, n-dodecyl group, chloroethyl group, trichloroethyl group, methoxyethyl group, ethoxyethyl group, phenoxyethyl group, benzyl group, phenethyl group, p-nitrobenzyl group, 4-methylphenethyl group, etc.), methanesulfonyl group or p-tolu It represents a Nsuruhoniru group. R ₁ is preferably an alkoxycarbonyl group having 2 to 9 carbon atoms, a methanesulfonyl group or a p-toluenesulfonyl group.

In the compound of the present invention represented by the formula (I), R ₁ protects the amino group during the subsequent reaction, while it is present in the coupler (dye) which is the target compound and has the function of improving the fastness.

In formula (I), Ar represents an unsubstituted phenyl group or a nitrophenyl group.

Specific examples of the compound represented by the above general formula used in the present invention are shown below, but the present invention is not limited thereto. The exemplary compound (7) is given as a reference and is not included in the present invention.

The compound of the present invention represented by the formula (I) is 5-amino-1.
-5-amino-1-naphthols 1 obtained by alkali melting of naphthalene sulfonic acids or 5-amino-1-naphthol-2-carboxylic acids 4 obtained by further performing a Kolbeschmitt reaction are used as raw materials as follows. It is carried out in a different scheme.

The reaction of steps (a) and (c) is carried out by subjecting compound 1 or 4 to chloroformate (ClCOOR ₁ ), sulfonyl chloride (R ₁ S
O ₂ Cl) or sulfonic anhydride (R ₁ SO ₂ ) ₂ O is allowed to act to give compound 2 or compound 5 . At this time, a weak base such as pyridine, tetramethylurea, tetramethylguanidine, or imidazole may be used as the base. The reaction is carried out in a nitrogen atmosphere.

The amount of chloroformic acid ester, sulfonyl chloride or sulfonic anhydride used is 0.1 to 5 relative to compound 1 or 4 .
The equivalent (molar ratio) is preferably 0.5 to 1.5 equivalents, and when a base is used, it is 0.1 to 10 equivalents, preferably 0.5 to 5 equivalents, relative to compound 1 or 4 . The reaction temperature is -50 ° C to 150 ° C.

In step (b), dichloromethane, chloroform, 1,2-
The reaction is carried out by allowing aryl chloroformate to act on Compound 2 using AlCl ₃ , FeCl ₃ or TiCl ₄ as a catalyst in a solvent such as dichloroethane, chlorobenzene or nitrobenzene. The amount of chloroformate aryl for 1 to 10 equivalents, preferably 2 1 to 7 equivalents. The amount of catalyst used is 1 to 2
10 equivalents, preferably 2-5 equivalents. Reaction temperature is 0-20
0 ° C is preferably 30 to 120 ° C. AlCl ₃ is preferred as the catalyst.

Acetonitrile In step (d), dimethyl formamide, compound 5 and phenol in a solvent such as dimethylacetamide, to give a compound 3 by condensation reaction with thionyl chloride or phosphorus oxychloride and naphthols.
However, a condensing agent such as dicyclohexylcarbodiimide or carbonyldiimidazole may be used instead of thionyl chloride. The amount of thionyl chloride, phosphorus oxychloride or condensing agent used is 0.1 to 10 equivalents, preferably 0.5 to 2 equivalents, relative to 5 . The amount of phenol or naphthol used relative to 5 is 0.5 to 3 equivalents, preferably 0.8.
~ 1.5 equivalents. The reaction temperature is -50 ° C to 150 ° C, preferably 0 ° C to 100 ° C.

(Effect of the Invention) The compound of the present invention is useful as a synthetic intermediate for a 5-substituted amino-1-naphthol type coupler which forms an indophenol dye excellent in performance such as fastness to heat. According to this compound, a 5-substituted amino-1-naphthol type coupler and an indophenol dye derived therefrom can be synthesized with a small number of steps and at low cost.

(Example) Next, the present invention will be described in more detail based on examples.

Example 1 Synthesis of Exemplified Compound (3) 79.6 g (0.5 mol) of 5-amino-1-naphthol was dissolved in 500 ml of dimethylacetamide and heated to 50 ° C. under a nitrogen stream to obtain 68.3 g (0.5 mol) of isobutyl chloroformate. Dropped. After heating and stirring for 3 hours, pour the reaction solution into water of 1 and
It was extracted with 0 ml of ethyl acetate. After distilling off ethyl acetate, crystallization with a mixed solvent of ethyl acetate-n-hexane yielded 108.9 g (yield 84%) of 5-isobutoxycarbonylamino-1-naphthol. The melting point was 114-115.5 ° C.

Next, under a nitrogen stream, 93.9 g (0.6 mol) of phenyl chloroformate and 80.0 g (0.6 mol) of aluminum chloride were added to 50 ml of dichloromethane.
It was dissolved in 0 ml. 5-Isobutoxycarbonylamino-1-naphthol (51.9 g, 0.2 mol) was added, and the mixture was stirred at 40 ° C. for 7 hours.
After refluxing for hours, it was cooled to room temperature and poured into 500 ml of ice water. Further, dichloromethane 1 was added, and the layers were separated,
The dichloromethane layer was taken out in a two-necked flask.
After distilling dichloromethane off under reduced pressure, 200 ml of ethyl acetate was added, the mixture was heated to 40 to 50 ° C., and 600 ml of acetonitrile was gradually added. The precipitated crystals were filtered to obtain phenyl 5-isobutoxycarbonylamino-1-hydroxy-2-naphthoate, that is, 56.9 g (yield 75%) of Exemplified compound (3). The melting point of this compound was 148.5-149.5 ° C.

Example 2 Synthesis of Exemplified Compound (1) Phenyl 1-hydroxy-5-methoxycarbonylamino-2-naphthoate in the same manner as in Example 1 except that methyl chloroformate was used instead of isobutyl chloroformate in Example 1. That is, exemplary compound (1) was obtained. The melting point of this compound was 172 to 173.5 ° C.

Example 3 Synthesis of Exemplified Compound (2) Phenyl 5-ethoxycarbonylamino-1-hydroxy-2-naphthoate was obtained in the same manner as in Example 1 except that ethyl chloroformate was used instead of isobutyl chloroformate in Example 1. That is, exemplary compound (2) was obtained. The melting point of this compound was 151-153 ° C.

Example 4 Separate Synthesis of Exemplified Compound (2) 5-Amino-1-hydroxy-2-naphthoic acid 40.6 g
(0.2 mol) is dissolved in 400 ml of dimethylacetamide,
Heated to 50 ° C under nitrogen stream, isobutyl chloroformate 27.3g
(0.2 mol) was added dropwise. After heating and stirring for 3 hours, the mixture was cooled to room temperature and 500 ml of water was added. The precipitated result was filtered, dried, and then dissolved in 500 ml of ethyl acetate and added with 10 g of activated carbon.
The mixture was heated under reflux for 30 minutes. After removing the activated carbon by filtration, about 2/3 of ethyl acetate was distilled off, 500 ml of acetonitrile was added, and the mixture was cooled. The precipitated result was filtered to obtain 59.1 g of 5-isobutoxycarbonylamino-1-hydroxy-2-naphthoic acid (yield 81%). The melting point of this compound is 2
It was from 05 to 208 ° C.

5-isobutoxycarbonylamino-1-hydroxy-
2-Naphthoic acid 30.3g (0.1mol) and phenol 9.4g
To (0.1 mol), 200 ml of acetonitrile and 2 ml of dimethylformamide were added, 15.0 g of thionyl chloride was added dropwise, and the mixture was heated under reflux for 3 hours. After cooling to room temperature and filtering the precipitated crystals, 33.4 g (yield 88%) of phenyl 5-isobutoxycarbonylamino-1-hydroxy-2-naphthoate, ie, Exemplified Compound (3), was obtained. The melting point of this compound is 1
It was 44-146 ° C.

Example 5 Synthesis of Exemplified Compound (4) 5-Isobutoxycarbonylamino-1-hydroxy-2-naphthoic acid 2 was prepared in the same manner as in Example 4 except that p-nitrophenol was used instead of phenol in Example 4. −
Nitrophenyl, ie, exemplary compound (4), was obtained in a yield of 81%. The melting point of this compound was 193-194 ° C.

Example 6 Synthesis of Exemplified Compound (5) 5-Amino-1-hydroxy-2-naphthoic acid 40.6 g
Dissolve (0.2 mol) in 400 ml of dimethylacetamide, heat to 50 ° C under a nitrogen stream, and wash with 2-ethylhexyl chloroformate.
38.5 g (0.2 mol) was added dropwise. After heating and stirring for 3 hours, the mixture was poured into water 1, extracted with 500 ml of ethyl acetate, and the ethyl acetate solution was washed twice with 500 ml of water. The ethyl acetate solution was dried over sodium sulfate, 10 g of activated carbon was added, and the mixture was heated under reflux for 30 minutes.
After removing the activated carbon by filtration, the ethyl acetate was distilled off,
500 ml of acetonitrile was added to the residue for crystallization. The precipitated crystals were filtered to obtain 60.0 g (yield 83.5%) of 5- (2-ethylhexyloxycarbonylamino-1-hydroxy-2-naphthoic acid. Melting point 170-
It was 173 ° C.

5- (2-ethylhexyloxycarbonylamino)-
1-hydroxy-2-naphthoic acid 18.0 g (0.05 mol),
Phenol 5.6g (0.06mol) and dimethylformamide
200 ml of acetonitrile was added to 2 ml, and 7.5 g (0.06 mol) of thionyl chloride was added dropwise with heating under reflux, and the mixture was heated under reflux for 2 hours.
By cooling the reaction solution and filtering the precipitated crystals, 5
-(2-Ethylhexyloxycarbonylamino) -1
18.9 g (yield 87%) of phenyl hydroxy-2-naphthoate, ie, the exemplified compound (5), was obtained. The melting point of this compound was 83 to 85 ° C.

Reference Example Synthesis of Exemplified Compound (7) 5-Amino-1-hydroxy-2-naphthoic acid 20.3 g
(0.1 mol) was dissolved in 200 ml of dimethylacetamide, and 15.7 g (0.1 mol) of phenyl chloroformate was added dropwise at 50 ° C under a nitrogen stream. After stirring for 4 hours, 500 ml of water was added and the mixture was extracted with 300 ml of ethyl acetate. The ethyl acetate solution was washed twice with 200 ml water. After drying the ethyl acetate solution over sodium sulfate, activated carbon 5g
Was added and the mixture was heated under reflux for 30 minutes. Activated carbon was removed by filtration and then concentrated, and 200 ml of acetonitrile was added for crystallization.
1-hydroxy-5 was obtained by filtering the precipitated crystals.
-Phenoxycarbonylamino-2-naphthoic acid 27.5 g
(Yield 85%) was obtained. The melting point of this compound was 225-26.5 ° C.

1-hydroxy-5-phenoxycarbonylamino-2
-Naphthoic acid 16.2 g (0.05 mol), phenol 5.2 g (0.0
(55 mol) and 2 ml of dimethylformamide, 200 ml of acetonitrile were added, 6.5 g (0.055 mol) of thionyl chloride was added dropwise with heating under reflux, and the mixture was heated under reflux for 2 hours. By cooling the reaction solution and filtering the precipitated crystals, 1-hydroxy-5-
16.2 g (yield 81%) of phenyl phenoxycarbonylamino-2-naphthoate, ie, exemplary compound (7), was obtained. The melting point of this compound was 172-175 ° C.

Example 7 Synthesis of Exemplified Compound (8) 1-Hydroxy-5- (2-methoxyethoxycarbonylamide) in the same manner as in Reference Example except that 2-methoxyethyl chloroformate was used instead of phenyl chloroformate in Reference Example. 2-Naphthoic acid was obtained with a yield of 89%. Melting point
It was 199-202 ° C. Further, in the same manner as in Reference Example, phenyl 1-hydroxy-5- (2-methoxyethoxycarbonylamido) -2-naphthoate, that is, Exemplified compound (8) was obtained at a yield of 75%. The melting point was 120-122 ° C.

Example 8 Synthesis of Exemplified Compound (11) 1-Hydroxy-5-trisulfonamido-2-naphthoic acid was obtained in the same manner as in Reference Example except that tosyl chloride was used instead of phenyl chloroformate in Reference Example.
Earned in%. The melting point was 230-231.5 ° C. Further, in the same manner as in Reference Example, phenyl 1-hydroxy-5-trisulfonamido-2-naphthoate, ie, Exemplified Compound (11), was obtained at a yield of 85%. The melting point was 249-251 ° C.

Example 9 Synthesis of Exemplified Compound (10) 1-Hydroxy-5-same as in Reference Example except that methylsulfonyl chloride was used instead of phenyl chloroformate and p-nitrophenol was used instead of phenol in Reference Example. P-Nitrophenyl methylsulfonamido-2-naphthoate was obtained with a yield of 83%.

The structures of these synthesized compounds are NMR spectra, MASS
Determined by spectrum and elemental analysis.

[Application example]

 The application examples of the compound of the present invention are shown below.

Application Example 1 Synthesis of Exemplified Coupler (3) Described in JP-A-60-237448 20.1 g (0.05 mole) of Exemplified Compound (10) of the present invention and 3-
(2,4-di-t-pentylphenoxy) propylamine 1
Acetonitrile (300 ml) was added to 6.0 g (0.055 mol), and the mixture was heated under reflux for 2 hours. The reaction solution was gradually stirred and cooled, and the precipitated crystals were filtered to give 5-methylsulfonamido-2- [N-3- (2,4-di-t-pentylphenoxy) propylcarbamoyl] -1-. Naphthol, that is, the exemplary coupler (3) described in JP-A-60-237448 is
5.8 g (yield 93%) was obtained. The melting point of this compound is 182-12.5.
It was ℃.

Application Example 2 Synthesis of Exemplified Compound (6) Described in JP-A-61-153640 17.6 g (0.05 mol) of Exemplified Compound (2) of the Present Invention and 3-
(2,4-di-t-pentylphenoxy) propylami 16.
300 ml of acetonitrile was added to 0 g (0.055 mol), and the mixture was heated under reflux for 3 hours. The reaction solution was gradually cooled with stirring, and the precipitated crystals were filtered to give 5-ethoxycarbonylamino-2- [N-3- (2,4-di-t-pentylphenoxy) -propylcarbamoyl] -1. -Naphthol, an exemplary coupler (6) described in JP-A-61-153640.
28.2 g (yield 89%) was obtained. The melting point of this compound is 135-13.
It was 7 ° C.

Application Example 3 Synthesis of Indophenol Dye 5.5 g of the exemplary coupler (3) synthesized in Application Example 1 (0.
Ethyl acetate (50 ml) and ethanol (50 ml) were added to the mixture (01 mol) and the mixture was stirred, potassium carbonate (13.8 g, 0.1 mol) in water (100 ml) was added, and 4- [N-ethyl-N- (2-methylsulfonamidoethyl) amino] was further added. 8.7 g of 2-methylaniline sulfate was added. 6.8 g of ammonium persulfate (0.
A solution of 03 mol) in 100 ml of water was added dropwise to separate the ethyl acetate layer. Ethyl acetate was distilled off, the mixture was developed using a silica gel-filled chromatographic column with ethanol-chloroform mixed solvent, the dye portion was fractionated and then concentrated, and the indophenol dye of the following structure was obtained by crystallization from acetonitrile. 5.9 g (yield 72%) was obtained. The melting point of this compound was 158 to 160.5 ° C., and the maximum absorption wavelength (λmax) in ethyl acetate injection was 675 mm and the maximum absorption coefficient (εmax) was 2.58 × 10 ⁴ .

Claims (1)

[Claims] 1. A 2-naphthoic acid aryl compound represented by the following formula. (In the formula, R ₁ represents an oxycarbonyl group or a sulfonyl group selected from the group consisting of an alkoxycarbonyl group having 2 to 13 carbon atoms, a methanesulfonyl group and a p-toluenesulfonyl group, and Ar represents an unsubstituted phenyl group or Represents a nitrophenyl group.)